CN110658319A - Method for detecting heavy metals in water - Google Patents
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- CN110658319A CN110658319A CN201910988585.5A CN201910988585A CN110658319A CN 110658319 A CN110658319 A CN 110658319A CN 201910988585 A CN201910988585 A CN 201910988585A CN 110658319 A CN110658319 A CN 110658319A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims description 34
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 82
- 239000011651 chromium Substances 0.000 claims abstract description 82
- 238000001514 detection method Methods 0.000 claims abstract description 46
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 4
- 238000005070 sampling Methods 0.000 claims abstract description 4
- 238000007781 pre-processing Methods 0.000 claims abstract description 3
- 239000000523 sample Substances 0.000 claims description 58
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000010521 absorption reaction Methods 0.000 claims description 17
- 239000012086 standard solution Substances 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 15
- 238000002835 absorbance Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000008139 complexing agent Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 229920000742 Cotton Polymers 0.000 claims description 9
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 9
- 239000001509 sodium citrate Substances 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012488 sample solution Substances 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 6
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 5
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 5
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 5
- -1 1-hexyl-3-methylimidazole hexafluorophosphate Chemical compound 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- GORBWKHYCDIEIF-UHFFFAOYSA-N azanium;pyrrolidine;carbamodithioate Chemical compound [NH4+].NC([S-])=S.C1CCNC1 GORBWKHYCDIEIF-UHFFFAOYSA-N 0.000 claims description 4
- 238000005259 measurement Methods 0.000 claims description 4
- 238000001228 spectrum Methods 0.000 claims description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 49
- 238000004458 analytical method Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 16
- 239000002608 ionic liquid Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000003002 pH adjusting agent Substances 0.000 description 5
- 229960001484 edetic acid Drugs 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001287 electrothermal atomic absorption spectrometry Methods 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910021654 trace metal Inorganic materials 0.000 description 2
- HVCOBJNICQPDBP-UHFFFAOYSA-N 3-[3-[3,5-dihydroxy-6-methyl-4-(3,4,5-trihydroxy-6-methyloxan-2-yl)oxyoxan-2-yl]oxydecanoyloxy]decanoic acid;hydrate Chemical compound O.OC1C(OC(CC(=O)OC(CCCCCCC)CC(O)=O)CCCCCCC)OC(C)C(O)C1OC1C(O)C(O)C(O)C(C)O1 HVCOBJNICQPDBP-UHFFFAOYSA-N 0.000 description 1
- 206010003210 Arteriosclerosis Diseases 0.000 description 1
- 229930186217 Glycolipid Natural products 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- VSWDORGPIHIGNW-UHFFFAOYSA-N Pyrrolidine dithiocarbamic acid Chemical compound SC(=S)N1CCCC1 VSWDORGPIHIGNW-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 150000007513 acids Chemical class 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 208000011775 arteriosclerosis disease Diseases 0.000 description 1
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- 239000007853 buffer solution Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 231100000433 cytotoxic Toxicity 0.000 description 1
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- 230000007812 deficiency Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
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- 239000000839 emulsion Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
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- 239000011573 trace mineral Substances 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/1813—Specific cations in water, e.g. heavy metals
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention relates to a detection method of heavy metals in water, relating to the technical field of analysis and detection, and comprising the following detection steps: s1: water sample collection: sampling a water body to be measured by using a sampler to obtain a water body sample; s2: adding a pH regulator into the obtained water body sample, regulating the pH value to 2-4, stirring and heating to 40 ℃, and filtering the water body sample; s3: preprocessing the water sample in S2; s4: and (4) determining the type and content of heavy metal chromium in the sample to be analyzed. By pretreating the water body sample in S3, the hexavalent chromium and the trivalent chromium in the water body can be pre-separated and enriched, so that the content of the hexavalent chromium and the trivalent chromium existing in trace amount in the water body can be detected conveniently.
Description
Technical Field
The invention relates to the technical field of analysis and detection, in particular to a method for detecting heavy metals in water.
Background
Chromium is a VIB group element, has an average content of 0.010-0.011 percent in the earth crust and mainly exists in the forms of trivalent chromium and hexavalent chromium. Studies have shown that chromium behaves as an essential element or as a harmful element, the valence state of which plays a decisive role. Trivalent chromium is a necessary trace element for human body, is indispensable for normal glycolipid metabolism, and chromium deficiency can cause arteriosclerosis and other diseases. But high concentrations of trivalent chromium still exhibit cytotoxic reactions. Hexavalent chromium has a strong toxicity, can damage DNA of human and animals, and is one of the identified carcinogens. Chromium has a wide range of applications and is commonly used in leather, printing and dyeing, electroplating, steel and other industries. Due to the discharge of a large amount of waste water, the content of chromium in water is increasing day by day, and the water environment is seriously polluted. Therefore, the analysis of toxic forms of chromium becomes important.
At present, methods related to detecting metal ions include methods such as Flame Atomic Absorption (FAAS), inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma emission spectroscopy (ICP-OES), electrothermal atomic absorption spectroscopy (ETAAS) and the like.
However, the direct detection of the water body by using the detection means has many problems, because the metal chromium in the water body exists in trace amount, the direct detection of the water body is easy to cause that the content of the heavy metal chromium cannot reach the detection limit, and the content of the metal chromium cannot be determined.
Disclosure of Invention
The invention aims to provide a method for detecting heavy metals in water, which is convenient for detecting the content of trace metal chromium in water.
The above object of the present invention is achieved by the following technical solutions:
a method for detecting heavy metals in water comprises the following detection steps:
s1: water sample collection: sampling a water body to be measured by using a sampler to obtain a water body sample;
s2: adding a pH regulator into the obtained water body sample, regulating the pH value to 2-4, stirring and heating to 40 ℃, and filtering the water body sample;
s3: preprocessing the water sample in S2;
s4: and (4) determining the type and content of heavy metal chromium in the sample to be analyzed.
By adopting the technical scheme, the trivalent chromium is easily adsorbed in suspended matters and particles in the water body, and the trivalent chromium can generate certain precipitation when the pH value is about 4.6. The pH regulator is added into the water body to regulate the pH value to 2-4 so as to dissolve out trivalent chromium in suspended matters and particles adsorbed in the water body, prevent the trivalent chromium from precipitating and improve the accuracy of data detection. And when the pH value of the complex of the trivalent chromium is 2-4, the state is stable, and the complex is not easy to be extracted by an extracting agent, so that the data detection of the hexavalent chromium can not be influenced by the trivalent chromium. The temperature is heated to 40 ℃ to accelerate the dissolution speed of the trivalent chromium and improve the detection efficiency. Meanwhile, the influence on the stability between the trivalent chromium and the hexavalent chromium and the conversion between the hexavalent chromium and the trivalent chromium caused by the overhigh temperature is prevented, and the accuracy of data detection is influenced. And can get rid of water suspended solid, particulate matter, reduce the turbidity, avoid the accuracy that the suspended solid in the water influences data detection. And S3, the method is used for pre-treating a water body sample, so that hexavalent chromium and trivalent chromium in the water body can be pre-separated and enriched, and the content of trace hexavalent chromium and trace trivalent chromium in the water body can be conveniently detected.
The invention is further configured to: the pretreatment comprises the following detection steps: measuring 1-5ml of filtered water body sample, adding 2-4 ml of complexing agent, uniformly stirring for 10-20min, heating in 40 ℃ constant temperature water bath for 15-20min, cooling to room temperature, rapidly adding 1-3ml of extracting agent and 1-3ml of dispersing agent into the sample solution, uniformly stirring, centrifuging the mixed solution at the rotation speed of 4000rpm for 2min, and taking supernatant to obtain the sample to be analyzed.
By adopting the technical scheme, the complexing agent is added firstly for pre-separating and enriching the hexavalent chromium and the trivalent chromium in the water body, so that the content of the hexavalent chromium and the trivalent chromium existing in trace in the water body can be conveniently detected. The dispersing agent is added, so that the extracting agent is uniformly dispersed in the solution in a microdroplet form to form emulsion, the contact area of the extracting agent and the sample solution is increased, the target analyte is quickly extracted into the microdroplet of the extracting agent, and then the extracting agent dispersed in the solution is deposited to the bottom of a test tube through centrifugation. The ionic liquid aqueous two-phase extraction is adopted, so that hexavalent chromium in the sample can be further separated and enriched, the detection limit of the method is reduced, and the sensitivity of the method is improved.
The invention is further configured to: the complexing agent comprises the following raw materials in percentage by weight: 40-60% of ethylenediamine tetraacetic acid and 40-60% of pyrrolidine ammonium dithiocarbamate.
By adopting the technical scheme, the ethylene diamine tetraacetic acid can be complexed with trivalent chromium to form a stable complex. And the pyrrolidine ammonium dithiocarbamate can be complexed with hexavalent chromium to form a stable complex. The hexavalent chromium and the trivalent chromium in the water body are pre-separated and enriched by the compound use of the hexavalent chromium and the trivalent chromium, so that the content of trace hexavalent chromium and trace trivalent chromium in the water body can be conveniently detected. The concentration of the ethylene diamine tetraacetic acid is 100mg/L, and the concentration of the ammonium pyrrolidine dithiocarbamate is 10 g/L.
The invention is further configured to: the pH regulator comprises the following raw materials in percentage by weight: 10-20% of nitric acid, 6-10% of sodium citrate, 6-10% of sodium dihydrogen phosphate, 10-20% of hydrochloric acid, 6-10% of hypochlorous acid and the balance of deionized water.
By adopting the technical scheme, hexavalent chromium is easily reduced into trivalent chromium under an acidic condition, and the reduction of the hexavalent chromium is prevented by adding hypochlorous acid, so that the detection accuracy of the trivalent chromium and the hexavalent chromium in water is improved. Sodium citrate is added to prevent the trivalent chromium from being oxidized, thereby improving the detection accuracy of the trivalent chromium and the hexavalent chromium in the water. Nitric acid and hydrochloric acid are both strong acids, which facilitates adjustment of the pH of the solution. The disodium hydrogen phosphate can improve the migration speed and the migration quantity of the trivalent chromium from the suspended matters, thereby improving the detection accuracy of the trivalent chromium and the hexavalent chromium in the water. Meanwhile, sodium citrate and disodium hydrogen phosphate can be complexed with trivalent chromium and hexavalent chromium to a certain extent, so that the trivalent chromium and the hexavalent chromium are prevented from being oxidized or reduced, and the detection accuracy of the trivalent chromium and the hexavalent chromium in the water is further improved. And the preseparation and enrichment of hexavalent chromium and trivalent chromium in the water body can be realized, so that the content of trace hexavalent chromium and trivalent chromium in the water body can be conveniently detected. The sodium citrate and the disodium hydrogen phosphate can be compounded to form a buffer solution for stabilizing the pH value of a water body sample.
The invention is further configured to: the extractant comprises the following raw materials in percentage by weight: 24-26% of 1-hexyl-3-methylimidazole hexafluorophosphate, 24-26% of disodium hydrogen phosphate, 6-10% of ammonium chloride and the balance of deionized water.
By adopting the technical scheme, the 1-hexyl-3-methylimidazolium hexafluorophosphate is ionic liquid, the disodium hydrogen phosphate is inorganic salt, the trace metal chromium in the water is enriched by adopting ionic liquid-inorganic salt aqueous two-phase extraction, the emulsification phenomenon is avoided, the phase separation can be completed within 2min, and the detection efficiency and accuracy are improved. And the used disodium hydrogen phosphate can be recycled and reused, and has the advantages of simple and convenient operation and low analysis cost. And the disodium hydrogen phosphate can be complexed with trivalent chromium, so that the trivalent chromium is prevented from entering supernatant liquid during layering, and the detection accuracy of hexavalent chromium is further influenced. The ammonium chloride can be used as a cosolvent to improve the solubility of hexavalent chromium in the ionic liquid, can be used as an inhibitor of coexisting elements, and can also inhibit the interference of CO, Fe, Ni, V, Pb and Mg.
The invention is further configured to: the dispersant comprises one or more of acetone, methanol and ethanol, preferably 40-60% of ethanol and 40-60% of methanol.
By adopting the technical scheme, the ionic liquid is more thoroughly dispersed in the methanol, and the extraction is more facilitated. However, methanol has certain toxicity, and the toxicity of the dispersing agent is reduced while the dispersing effect of the ionic liquid is improved by compounding ethanol and methanol, so that the subsequent waste liquid treatment is facilitated.
The invention is further configured to: adopt the PP cotton to filter among the S2 to observe the PP cotton after filtering, can tentatively judge the pollution concentration condition of water sample according to the depth degree of PP cotton colour.
Through adopting above-mentioned technical scheme, can tentatively judge the pollution concentration condition of water sample, the judgement of the later detection data accuracy of being convenient for, the experimenter of being convenient for operates.
The invention is further configured to: the S4 includes the following detecting steps:
1) preparing a series of standard solutions with different concentrations by taking a plurality of different heavy metals, and performing pretreatment in S3 on the prepared standard solutions to prepare standard solutions to be detected;
2) performing flame atomic absorption spectrophotometer measurement on the standard solution to be measured to obtain absorbances of different heavy metals and different concentrations, and drawing a concentration-absorbance standard curve of the heavy metals according to the concentration, wherein each element corresponds to one standard curve;
3) carrying out flame atomic absorption spectrophotometer determination on a sample to be analyzed;
4) and comparing the absorbance of the sample to be analyzed with the absorbance of the standard solution to obtain the type and the content of the heavy metal in the sample to be analyzed.
The invention is further configured to: the flame atomic absorption spectrophotometer uses a chromium cathode lamp, and the parameters of the flame atomic absorption spectrophotometer are set as follows: lamp current 5mA, wavelength 357.9nm, spectrum 0.7nm, air pressure 0.1MPa, air flow 15L/min, acetylene pressure 0.13MPa, acetylene flow 2.8L/min, burner height 10 mm.
By adopting the technical scheme, the method is used for carrying out quantitative and qualitative analysis on the hexavalent chromium of the water body sample. And the parameters of the flame atomic absorption spectrophotometer are set as shown above, so that the detection sensitivity and accuracy of the flame atomic absorption spectrophotometer can be improved.
The invention is further configured to: the pretreatment comprises the following detection steps: measuring 1-5ml of filtered water body sample, adding 2-4 ml of complexing agent, stirring uniformly for 10-20min, dropwise adding ammonia water, adjusting the pH value to 6-7, heating in 80 ℃ constant-temperature water bath for 15-20min, cooling to room temperature, quickly adding 1-3ml of extracting agent and 1-3ml of dispersing agent into the sample solution, stirring uniformly, centrifuging the mixed solution at the rotation speed of 4000rpm for 2min, and taking supernatant to obtain the sample to be analyzed.
By adopting the technical scheme, when the pH value is 6-7 and the heating temperature is 80 ℃, the complex of trivalent chromium and hexavalent chromium can be completely extracted, and the amount of the trivalent chromium can be detected by subtracting the amount of the hexavalent chromium from the amount of the total metal chromium, so that the operation of detection personnel is facilitated, and the detection efficiency is improved. The mass concentration of the ammonia water is 20%.
In conclusion, the beneficial technical effects of the invention are as follows:
1. the pH regulator is added into the water body to regulate the pH value to 2-4 so as to dissolve out trivalent chromium in suspended matters and particles adsorbed in the water body, prevent the trivalent chromium from precipitating and improve the accuracy of data detection;
2. by pretreating the water body sample in S3, the hexavalent chromium and the trivalent chromium in the water body can be pre-separated and enriched, so that the content of trace hexavalent chromium and trace trivalent chromium in the water body can be conveniently detected;
3. the nitric acid, the sodium citrate, the sodium dihydrogen phosphate, the hydrochloric acid and the hypochlorous acid are used in a compounding manner to adjust the pH value of a water body sample and prevent hexavalent chromium reduction and trivalent chromium oxidation, so that the detection accuracy of the trivalent chromium and the hexavalent chromium in water is improved, and the pre-separation and enrichment of the hexavalent chromium and the trivalent chromium in the water body can be realized, so that the content of trace hexavalent chromium and trivalent chromium in the water body can be conveniently detected.
Detailed Description
The first embodiment is as follows:
the invention discloses a method for detecting heavy metals in water, which comprises the following detection steps:
s1: water sample collection: sampling a water body to be measured by using a sampler to obtain a water body sample;
s2: adding a pH regulator into the obtained water sample, regulating the pH value to 2, stirring and heating to 40 ℃, filtering the water sample by using PP cotton, observing the filtered PP cotton, and preliminarily judging the pollution concentration condition of the water sample according to the depth of the PP cotton;
preparing a pH regulator: uniformly mixing 10% of nitric acid, 6% of sodium citrate, 6% of sodium dihydrogen phosphate, 10% of hydrochloric acid, 6% of hypochlorous acid and 50% of deionized water to prepare a pH regulator;
s3: the following processing is performed on the water sample in S2: measuring 1ml of filtered water body sample, adding 2ml of complexing agent, stirring uniformly for 10min, heating in 40 ℃ constant-temperature water bath for 15min, cooling to room temperature, quickly adding 1ml of extracting agent and 1ml of dispersing agent into the sample solution, stirring uniformly, centrifuging the mixed solution at the rotating speed of 4000rpm for 2min, and taking supernatant to obtain a sample to be analyzed;
preparing a complexing agent: uniformly mixing 40% of ethylenediamine tetraacetic acid and 60% of pyrrolidine ammonium dithiocarbamate to prepare a complexing agent;
preparing an extracting agent: uniformly mixing 24% of 1-hexyl-3-methylimidazolium hexafluorophosphate, 26% of disodium hydrogen phosphate, 6% of ammonium chloride and 57% of deionized water to prepare an extracting agent;
preparing a dispersing agent: uniformly mixing 40% ethanol and 60% methanol to prepare a dispersing agent;
s4: the method for determining the type and the content of the heavy metal chromium in the sample to be analyzed comprises the following detection steps:
1) preparing a series of standard solutions with different concentrations by taking a plurality of different heavy metals, and performing pretreatment in S3 on the prepared standard solutions to prepare standard solutions to be detected;
2) performing flame atomic absorption spectrophotometer measurement on the standard solution to be measured to obtain absorbances of different heavy metals and different concentrations, and drawing a concentration-absorbance standard curve of the heavy metals according to the concentration, wherein each element corresponds to one standard curve; the standard curve is drawn according to the heavy metal concentration in the standard solution from small to large;
3) carrying out flame atomic absorption spectrophotometer determination on a sample to be analyzed;
the flame atomic absorption spectrophotometer is an atomic absorption spectrophotometer with the model number of AA3510, which is produced by Shanghai precision instruments and meters company Limited; a chromium cathode lamp was used in the measurement, and the parameters of the flame atomic absorption spectrophotometer were set to: lamp current 5mA, wavelength 357.9nm, spectrum 0.7nm, air pressure 0.1MPa, air flow 15L/min, acetylene pressure 0.13MPa, acetylene flow 2.8L/min, burner height 10 mm;
4) and comparing the absorbance of the sample to be analyzed with the absorbance of the standard solution to obtain the content of the hexavalent chromium in the sample to be analyzed.
When the concentration of trivalent chromium is to be measured, S3 includes the following detection steps:
1) measuring two parts of filtered water samples with the volume of 1ml respectively, adding 2ml of complexing agent into the two parts of water samples respectively, and stirring for 10 min;
2) adding ammonia water with the mass concentration of 20% into one group of water body samples, adjusting the pH value to 6, heating in a constant-temperature water bath at 80 ℃ for 15min, cooling to room temperature, quickly adding 1ml of an extracting agent and 1ml of a dispersing agent into the sample solution, stirring uniformly, centrifuging the mixed solution at the rotating speed of 4000rpm for 2min, and taking supernatant to obtain a sample A to be analyzed;
3) heating the rest group of water samples in a constant-temperature water bath at 40 ℃ for 15min, cooling to room temperature, quickly adding 1ml of extracting agent and 1ml of dispersing agent into the sample solution, uniformly stirring, centrifuging the mixed solution at the rotation speed of 4000rpm for 2min, and taking supernatant to obtain a sample B to be analyzed;
4) respectively measuring a sample A to be analyzed and a sample B to be analyzed by a flame atomic absorption spectrophotometer, and comparing the absorbance of the sample A to be analyzed and the absorbance of the sample B to be analyzed with the standard solution to obtain the total chromium content in the sample A to be analyzed and the hexavalent chromium content in the sample B to be analyzed;
5) the content of trivalent chromium can be obtained by subtracting the content of hexavalent chromium from the content of total chromium, so that the operation of detection personnel is facilitated, and the detection efficiency is improved.
The water used in the present invention is deionized water.
Examples 2 to 5 differ from example 1 in that the pH adjusting agent in S2 comprises the following raw materials in weight percent:
examples 6 to 9 differ from example 1 in that the pH values of the adjusted water body samples in S2 are shown in the following table:
| examples | Example 6 | Example 7 | Example 8 | Example 9 |
| pH value | 2.5 | 3 | 3,5 | 4 |
Examples 10-13 differ from example 1 in that the water sample values in S3 are shown in the following table:
| examples | Example 10 | Example 11 | Example 12 | Example 13 |
| Volume/ml | 2 | 3 | 4 | 5 |
Examples 14-17 differ from example 1 in that the complexing agent was added in the amount shown in the table below in S3:
| examples | Example 14 | Example 15 | Example 16 | Example 17 |
| Addition amount/ml | 2.5 | 3 | 3,5 | 4 |
Examples 18-21 differ from example 1 in that the mixing time after addition of the complexing agent in S3 is as shown in the following table:
| examples | Example 18 | Example 19 | Example 20 | Example 21 |
| While stirringTime to min | 13 | 15 | 17 | 20 |
Examples 22-25 differ from example 1 in that the water bath heating time in S3 is as shown in the following table:
| examples | Example 22 | Example 23 | Example 24 | Example 25 |
| Heating time/min | 16 | 17 | 18 | 20 |
Examples 26-29 differ from example 1 in that the amount of extractant added in S3 is shown in the following table:
| examples | Example 26 | Example 27 | Example 28 | Example 29 |
| Addition amount/ml | 1.5 | 2 | 2.5 | 3 |
Examples 30 to 33 differ from example 1 in that the amount of dispersant added in S3 is shown in the following table:
| examples | Example 30 | Example 31 | Example 32 | Example 33 |
| Addition amount/ml | 1.5 | 2 | 2.5 | 3 |
Examples 34-37 differ from example 1 in that the complexing agent in S3 comprises the following raw materials in weight percent:
examples 38-41 differ from example 1 in that the extractant in S3 comprises the following raw materials in weight percent:
examples 42 to 47 differ from example 1 in that the dispersant in S3 comprises the following raw materials in weight percent:
examples 48 to 51 differ from example 1 in that the pH values at which trivalent chromium is measured in S3 are shown in the following table:
| examples | Example 48 | Example 49 | Example 50 | Example 51 |
| pH value | 6.3 | 6.5 | 6.7 | 7 |
Comparative example:
comparative example 1 differs from example 1 in that the detection method does not involve S3: pre-treating;
comparative example 2 is different from example 1 in that no pH adjuster is added in S2 in the detection method;
comparative example 3 is different from example 1 in that heating is not performed in S2 in the detection method;
comparative example 4 is different from example 1 in that the pH adjusting agent in S2 in the detection method is nitric acid;
comparative example 5 differs from example 1 in that the pH adjuster is free of sodium citrate;
comparative example 6 differs from example 1 in that no sodium dihydrogen phosphate is present in the pH adjuster.
Surface water containing total chromium with mass concentration of 0.019mg/L respectively is used as a detection sample, wherein hexavalent chromium accounts for 70% of the total chromium, the mass concentration of a scalar is 0.2mg/L, and the method for detecting the standardized recovery rate of the hexavalent chromium in the soil is adopted in the embodiments 1-3 and the comparative examples 1-4.
| Examples | Total chromium recovery rate | Recovery rate of hexavalent chromium by adding standard |
| Example 1 | 97.4％ | 98.6％ |
| Example 2 | 97.5％ | 98.8％ |
| Example 3 | 97.7％ | 99.1％ |
| Comparative example 1 | Is unable to detect | Is unable to detect |
| Comparative example 2 | 94.6％ | 95.7％ |
| Comparative example 3 | 96.9％ | 98.2％ |
| Comparative example 4 | 97.1％ | 97.5％ |
| Comparative example 5 | 97.2％ | 99.4％ |
| Comparative example 6 | 96.6％ | 98.3％ |
As can be seen from the above table, the comparison between examples 1 to 3 and comparative example 1 shows that the hexavalent chromium and the trivalent chromium in the water can be pre-separated and enriched by pre-treating the water sample, so that the content of trace hexavalent chromium and trace trivalent chromium in the water can be conveniently detected. As can be seen from comparison between examples 1-3 and comparative examples 2-6, the pH regulator is added into the water body and heated to 40 ℃ so as to dissolve out trivalent chromium in suspended matters and particles adsorbed in the water body, prevent the trivalent chromium from precipitating and improve the accuracy of data detection. By adding hypochlorous acid, hexavalent chromium is prevented from being reduced, so that the detection accuracy of trivalent chromium and hexavalent chromium in water is improved. Sodium citrate is added to prevent the trivalent chromium from being oxidized, thereby improving the detection accuracy of the trivalent chromium and the hexavalent chromium in the water. The disodium hydrogen phosphate is added, so that the migration speed and the migration quantity of the trivalent chromium from the suspended matters can be improved, and the detection accuracy of the trivalent chromium and the hexavalent chromium in water is improved.
The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all equivalent changes made according to the structure, shape and principle of the invention are covered by the protection scope of the invention.
Claims (10)
1. A method for detecting heavy metals in water is characterized by comprising the following steps: the method comprises the following detection steps:
s1: water sample collection: sampling a water body to be measured by using a sampler to obtain a water body sample;
s2: adding a pH regulator into the obtained water body sample, regulating the pH value to 2-4, stirring and heating to 40 ℃, and filtering the water body sample;
s3: preprocessing the water sample in S2;
s4: and (4) determining the type and content of heavy metal chromium in the sample to be analyzed.
2. The method for detecting the heavy metal in the water according to claim 1, wherein the method comprises the following steps: the pretreatment comprises the following detection steps: measuring 1-5ml of filtered water body sample, adding 2-4 ml of complexing agent, uniformly stirring for 10-20min, heating in 40 ℃ constant temperature water bath for 15-20min, cooling to room temperature, rapidly adding 1-3ml of extracting agent and 1-3ml of dispersing agent into the sample solution, uniformly stirring, centrifuging the mixed solution at the rotation speed of 4000rpm for 2min, and taking supernatant to obtain the sample to be analyzed.
3. The method for detecting the heavy metal in the water according to claim 2, wherein the method comprises the following steps: the complexing agent comprises the following raw materials in percentage by weight: 40-60% of ethylenediamine tetraacetic acid and 40-60% of pyrrolidine ammonium dithiocarbamate.
4. The method for detecting the heavy metal in the water according to claim 2, wherein the method comprises the following steps: the pH regulator comprises the following raw materials in percentage by weight: 10-20% of nitric acid, 6-10% of sodium citrate, 6-10% of sodium dihydrogen phosphate, 10-20% of hydrochloric acid, 6-10% of hypochlorous acid and the balance of deionized water.
5. The method for detecting the heavy metal in the water according to claim 2, wherein the method comprises the following steps: the extractant comprises the following raw materials in percentage by weight: 24-26% of 1-hexyl-3-methylimidazole hexafluorophosphate, 24-26% of disodium hydrogen phosphate, 6-10% of ammonium chloride and the balance of deionized water.
6. The method for detecting the heavy metal in the water according to claim 2, wherein the method comprises the following steps: the dispersant comprises one or more of acetone, methanol and ethanol, preferably 40-60% of ethanol and 40-60% of methanol.
7. The method for detecting the heavy metal in the water according to claim 1, wherein the method comprises the following steps: adopt the PP cotton to filter among the S2 to observe the PP cotton after filtering, can tentatively judge the pollution concentration condition of water sample according to the depth degree of PP cotton colour.
8. The method for detecting the heavy metal in the water according to claim 1, wherein the method comprises the following steps: the S4 includes the following detecting steps:
1) preparing a series of standard solutions with different concentrations by taking a plurality of different heavy metals, and performing pretreatment in S3 on the prepared standard solutions to prepare standard solutions to be detected;
2) performing flame atomic absorption spectrophotometer measurement on the standard solution to be measured to obtain absorbances of different heavy metals and different concentrations, and drawing a concentration-absorbance standard curve of the heavy metals according to the concentration, wherein each element corresponds to one standard curve;
3) carrying out flame atomic absorption spectrophotometer determination on a sample to be analyzed;
4) and comparing the absorbance of the sample to be analyzed with the absorbance of the standard solution to obtain the type and concentration of the heavy metal chromium in the sample to be analyzed.
9. The method for detecting the heavy metal in the water according to claim 8, wherein the method comprises the following steps: the flame atomic absorption spectrophotometer uses a chromium cathode lamp, and the parameters of the flame atomic absorption spectrophotometer are set as follows: lamp current 5mA, wavelength 357.9nm, spectrum 0.7nm, air pressure 0.1MPa, air flow 15L/min, acetylene pressure 0.13MPa, acetylene flow 2.8L/min, burner height 10 mm.
10. The method for detecting the heavy metal in the water according to claim 1, wherein the method comprises the following steps: the pretreatment comprises the following detection steps: measuring 1-5ml of filtered water body sample, adding 2-4 ml of complexing agent, uniformly stirring for 10-20min, adding ammonia water, adjusting the pH value to 6-7, heating in 80 ℃ constant-temperature water bath for 15-20min, cooling to room temperature, rapidly adding 1-3ml of extracting agent and 1-3ml of dispersing agent into the sample solution, uniformly stirring, centrifuging the mixed solution for 2min at the rotation speed of 4000rpm, and taking supernatant to obtain the sample to be analyzed.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114414509A (en) * | 2021-12-30 | 2022-04-29 | 通标标准技术服务（天津）有限公司 | Method for detecting heavy metal chromium in food |
| CN116969552A (en) * | 2023-09-21 | 2023-10-31 | 贵州勘设生态环境科技有限公司 | Integrated sewage treatment control and regulation system and device thereof |
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